JPH04503081A - Fluoropolymer composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Fluoropolymer composition The present invention relates to laser markable fluoropolymer compositions and coatings coated with the compositions. articles, such as electrical conductors, shaped articles formed from the composition, especially heat recoverable Articles, methods for making fluoropolymers laser markable, and labels The present invention relates to a method for forming marks on a fluoropolymer surface using a laser.

Difficult to create marks on fluoropolymers using traditional printing methods It is known. Fluoropolymer surfaces, e.g. fluoropolymer wires Marks on jackets or cable jackets or marker sleeves, etc. It is often preferable to do so.

The use of lasers to form marks on polymeric articles has been described in the literature. has been done. For example, U.S. Pat. No. 4,307,047 [Edinger (E Dinger) Fillers that can change color, such as iron oxides/hydroxides Marking type plate molded from plastic material such as ABS containing Turkey is disclosed. In U.S. Patent No. 4.118.229 , Stromberger-Dalton-Rauha (S tromberger-D'A (1ton-Rauch) et al. used a laser beam to produce acetylacetone. Discloses recording visible data in a polymer layer containing sheets. Candy No. 4,443,571, Needham have used lasers to detect additive systems such as nickel-antimony-titanium. , or a polyarylene sulfide composition containing a monoazo-nickel complex It is disclosed that a mark is formed on the mark. Various additives, such as glass fibers, It is stated that it contains talc, titanium dioxide, silica or calcium sulfate. It is. United States Patent No. 4.654.290 [Spanger (Sp resin (e.g. epoxy, silicone or polyimide) , titanium dioxide, and inorganic additives that may or may not be present (e.g., acid Marking by laser on compositions containing chromium chloride or carbon black) It is disclosed that the formation of The composition contains fillers, e.g. aluminum oxide and silicon oxide. Australian Patent Application No. 52821/8 No. 6 [Gugger et al.] contains a radiation-sensitive additive that changes color. discloses the formation of marks by laser in various polymers. example For example, the additive may be an inorganic or organic pigment or a polymeric soluble dye.

None of these references mention fluoropolymers and therefore laser does not suggest a fluoropolymer composition capable of forming marks by It also suggests that fluoropolymers can be made markable by lasers. do not have.

According to one aspect, the present invention provides fluoropolymer resins having a processing temperature of about 250°C or higher. reamer, about 2-7% by weight based on the weight of the fluoropolymer. 1 to 1 based on the weight of the fluoropolymer. 5% by weight with mark enhancement having a decomposition temperature above the processing temperature of the fluoropolymer. a laser that contains organic compounds and that can undergo a visible color change when exposed to the laser; - Provides a mark-formable composition.

According to another aspect, the present invention provides a fluoropolymer having a processing temperature of about 250° C. or higher. energy from the laser, approximately 2 to 7% by weight based on the weight of the fluoropolymer. 1 to 1 based on the weight of the fluoropolymer. 5% by weight with mark enhancement having a decomposition temperature above the processing temperature of the fluoropolymer. A fluorophore containing organic compounds that can undergo a visible color change when exposed to a laser. An article having a surface coated with a polypolymer composition is provided.

According to yet another aspect, the present invention provides a method for fluorocarbons having a processing temperature of about 250° C. or higher. from about 2 to 7% by weight based on the weight of the fluoropolymer. Compound capable of absorbing energy, and approximately 1 based on the weight of the fluoropolymer ~15% by weight of a mark increase having a decomposition temperature above the processing temperature of the fluoropolymer. A heat recoverable article comprising a strong organic compound is provided.

According to another aspect, the present invention provides a fluoropolymer and a fluoropolymer by weight. about 2-7% by weight of a compound capable of absorbing energy from a laser based on Addition of about 1 to 15% by weight of the fluoropolymer, based on the weight of the fluoropolymer. does not include mixing mark-enhancing organic compounds with a decomposition temperature above the decomposition temperature. A method of making a fluoropolymer markable by a laser is provided.

According to yet another aspect, the present invention provides a fluoropolymer composition comprising: Capable of absorbing energy from about 2-7% of the laser based on the weight of the laser about 1-15% by weight, based on the weight of the fluoropolymer, and the fluoropolymer. containing a mark-enhancing organic compound having a decomposition temperature higher than the processing temperature of the polymer; a fluoropolymer composition comprising exposing a surface of the composition to a laser. A method of forming a mark on a surface comprising:

Fluoropolymers suitable for use in the present invention include thermoplastic fluoropolymers. polymers and elastomeric fluoropolymers, specifically homologous tetrafluoroethylene. Polymers and copolymers such as polytetrafluoroethylene, ethylene/ Tetrafluoroethylene copolymer, tetrafluoroethylene/propylene copolymer remer; homopolymers and copolymers of vinylidene fluoride, e.g. Rivinylidene fluoride, vinylidene fluoride/hexafluoropropylene Copolymer, vinylidene fluoride/tetrafluoroethylene/hexaflu Olopropylene terpolymer; perfluoroalkoxy polymer, fluorinated ethylene lene/propylene copolymers and the like. A preferred fluoropolymer is ethyl ethylene/tetrafluoroethylene copolymer (ETFE).

The composition of the invention does not contain compounds capable of absorbing energy from the laser used. The amount is about 2-7% by weight based on the weight of the fluoropolymer. composition The energy absorber is about 2-5% by weight based on the weight of the fluoropolymer. , most preferably in an amount of about 2-4% by weight.

The energy absorber used depends, in part, on the laser used. For example, In the ozim/yttrium-sugar-garnet (Nd:YAG) laser, Titanium dioxide is a preferred energy absorber.

The addition of energy absorbers alone will cause the fluoropolymer to degrade when exposed to the laser. cannot form acceptable marks on the surface of the The composition of the present invention has specific A mark-enhancing organic compound with a decomposition temperature equal to or higher than the melt processing temperature of the fluoropolymer. It also includes. (Fluoropolymers generally have a temperature of about 220-400°C. Has high processing temperature. Commercially available ethylene preferred in the practice of this invention /tetrafluoroethylene copolymer has a melting temperature of about 220-280°C. Ru. ) Organic compounds alone confer laser mark formation potential on fluoropolymers. No. However, fluoropolymers containing energy absorbers and organic compounds - The composition can be easily marked by laser. Suitable organic compounds are , can be easily determined by a person skilled in the art. One determining mark-enhancing compound A rapid method selects compounds with decomposition temperatures above the processing temperature of the fluoropolymer. heat the compound to a temperature of about 400°C and observe whether it undergoes a visible color change. That's true. Typically, the compositions of the invention are light colored and the resulting laser marker The color is dark. Unlike the compositions of the present invention, energy absorbers or organic A composition comprising either one of the compounds or an inadequate amount of either the compound is , not easily marked by laser. mark such compositions If the laser energy output is adjusted to provide sufficient energy for fluoropolymer failure may occur.

The compositions of the present invention are capable of forming marks at fairly low energy levels and are The olopolymer composition will not be damaged.

Preferred organic compounds are sulfur-containing compounds, such as distearylthiodipropiodine. dilaurylthiodipropionate or oligomers thereof, 4.4° -thiobis(6-t-butyl-m-cresol); hydroxy-containing compounds, e.g. For example, tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl) henyl) propionate comethane, 2,2゛-oxamidobis(ethyl 3-( 3゜5-di-t-butyl-4-hydroxyphenyl)propionate, resorcy Normonoacetate; nitrogen-containing compounds, e.g. triallylisone anurate , triallylthoanurate, bis-melaminium bentate, acetylene diurene N, L-alanine, melamine, acetanilide, guanine, dibenzylamine , dibenzyldiphenylamine, 4,4'-bis(dimethylamino)-benzof Phosphorus-containing compounds, such as tetrakis(2,4-di-t-butylphenyl) )-4,4'-biphenylene diphosphonate, tris(2°4-di-t-butyl)-4,4'-biphenylene diphosphonate, (ruphenyl) phosphite, bis(2,4-di-t-butyl)pentaerythrite diphosphite, distearyl pentaerythritol diphosphate, tri- phenyl phosphate, triphenylphosphine oxyto; and carbonyl-containing compounds such as magnesium stearate, diphenylacetaldehyde, Includes ethyldimalonate and the like.

The compositions of the present invention contain about 1-15% by weight of organic compounds based on the weight of the fluoropolymer. Contains compounds. The composition consists of organic compounds based on the weight of the fluoropolymer. preferably in an amount of about 2-10% by weight, most preferably about 2-7% by weight. .

Various additives can be added to the polymer composition. Such additives are To illustrate, antioxidants, specifically alkylated phenols, e.g. Goodrite 3125, Irganox 1010. Irganox 1035, Irganox 1076, Irganox 1093, commercially available as Vulkanox BKF, Mechanical phosphites or phosphates, such as dilauryl phosphite, mark ( Mark) 178, alkylidene polyphenols, such as methanox ( Ethanox) 330, thiobisalkylated phenols, e.g. S antonox R, dilauryl thiodipropionate, e.g. Carstab DLTDP, Similistilthiodipropione such as Carstab DMTDP1 distearyl thiodipropionate, e.g. For example, Cyanox STDP, amines, such as Wingeste WingstaV 29, etc.; UV stabilizers, such as [2,2'-thio- bis(4-t-octyl-phenolad)]]n-butylamine nickel seeso Cyasorb UV 1084.3,5-di-t-butylhydroxy( phydroxy) benzoic acid, UV Check (Chek) AM-240; flame retardant , for example, decabromodiphenyl ether, perchloropentacyclodecane, 1 ．． 2-bis(tetrabromophthalimide)ethylene; pigments, e.g. tita dioxide These include antimony dioxide, zinc oxide, iron oxide, etc. of such additives Mixtures may also be used. Some of these additives, when present in said amounts, It can also function as an organic compound.

The compositions of the present invention include a fluoropolymer, an energy absorbing compound, and an organic compound. For example, an internal mixer such as a Banbury or a Brabender, a Brabender fluoropolymer in a twin screw extruder such as ZSK Temperatures above the melting temperature (or above the processing temperature if the fluoropolymer is elastic) can be prepared by mixing at a temperature of

The compositions of the invention can be crosslinked, if desired. Crosslinking can be carried out using a suitable crosslinking agent, e.g. by the use of oxides or amines or by irradiation, e.g. I can do it.

In a preferred embodiment, the composition is crosslinked by radiation. In the irradiation process The dose used is to ensure that the polymer does not deteriorate due to over-irradiation. , generally less than about 50 Mrad.

The dose used must be balanced against the tendency of the polymer to degrade with high-dose irradiation. However, it is preferred that it depends on the desired degree of crosslinking. Suitable doses generally range from 2 to 40M rads, such as 2-30M rads, preferably 3-20M rads, more preferably is between 4 and 25M rads or between 4 and 20M rads, especially between 4 and 15M rads. Ionizing rays are , for example, in the form of accelerated electrons or gamma rays. Irradiation is generally carried out in the chamber Although the process is carried out at high temperatures, higher temperatures may be used.

It is preferable that the composition contains a crosslinking agent before irradiation. Preferred irradiation crosslinking The agent contains carbon-carbon unsaturated groups. Often the cross-linking agent is e.g. allyl , metaallyl, propargyl or at least two ethyl groups which may be present in the vinyl group. It has a lentic double bond.

Preferred crosslinkers have at least two allyl groups, especially three or four allyl groups. has. Particularly preferred crosslinking agents are triallylcyanurate (TAC) and Realyl isocyanurate (TAIC). Other useful crosslinking agents include Allyl trimellitate, triallyl trimesade, tetraallyl pyromellitate , 1,1.3-trimethyl-5-carboxy-3-(p-carboxyphenyl) Includes diallyl esters of indane. contained in the fluorocarbon polymer before molding. Other crosslinking agents known to No. 3.222, No. 3.840.619, No. 3.894.118, No. 3,911,1 No. 92, No. 3,970.770, No. 3.985.716, No. 3.995,091 , No. 4,031,167, No. 4.155.823 and No. 4,353,961. This is what is described. Mixtures of crosslinking agents may be used. These crosslinking agents (Cucane can be used as an organic compound when present in appropriate amounts.

The composition can be formed into shapes by melt processing, lamination, extrusion or other suitable methods. It can be formed into products or coatings. A preferred use of the composition of the invention is for long electrical conductors. insulation for bodies, e.g. wires or cables. The composition is derived by extrusion. Covering the body is preferred, but other methods such as wrapping with tape may also be used. can be applied.

Another preferred use of the compositions of the invention is in heat recoverable articles, especially wires or cables. manufacturing of articles used as marker sleeves for Heat-recoverable articles are An article whose dimensions and shape can change when subjected to appropriate treatments.

Typically, upon heating, these articles recover toward their original shape before being pre-deformed. However, the term "thermal recovery" used in this specification has been previously transformed. However, it also includes articles that adopt a new shape when heated.

In its most common form, heat recoverable articles are described, for example, in U.S. Pat. 2.027.962, 3.086.242 and 3°597,372. Made from polymeric materials that exhibit elastic or plastic memory properties as listed. a heat-shrinkable sleeve. For example, U.S. Patent No. 2.027. As evident in No. 962, the original dimensionally heat-stable shape is e.g. extruded. The tube undergoes a continuous process in which it expands while hot into a dimensionally thermally unstable shape. may be a temporary shape, but in other cases a pre-formed dimensionally thermal A stable article may be transformed into a dimensionally thermolabile shape in a separate step.

In the manufacture of heat recoverable articles, polymeric materials are used to enhance the desired dimensional recoverability. It may be crosslinked (as described above) at any step in the manufacture of the article. heat recovery One method for making a polymeric article is to form the polymeric article into the desired heat-labile shape and to Cross-link the polymer material, heat the article to a temperature above the crystalline melting point of the polymer, and deform the article. and cooling the article in the deformed state to maintain the deformed state of the article. use , the deformed state of the article is thermally unstable, so heating returns the article to its original thermal stability. Trying to take a fixed shape.

The following examples illustrate the preparation and preparation of laser markable compositions of the invention. and the formation of marks on the composition by laser.

Ethylene/tetrafluoroethylene copolymer (ETFE) [Tef zel) HT-2055, DuPont commercial product], titanium dioxide, and organic The mixture was prepared in a Brabender twin screw mixer in the amounts shown in Table 1. The composition by mixing at 0 °C (all zones of the mixer) and 20 rpm was prepared. Organic compounds are: Irglolo=tetrakis[methylene-3-(3,5-di-t-butyl-4 -Hydroxyphenyl)propionate comethane [Irganox ox) 1010, Ciba-Geigy commercial product] DS-TDP = Distearylthiodipropionate [Evans Chemetic Available from Evans Chemetics. Irgaf 16g = Tris(2,4-di-t-butylphenyl)-4,4 ゛-Phosphite [I rgafos 168, Ciba Geigy Commercial product] TAIC = l-Reallyl isocyanurate Takubi Each test sample was pressed to 0.025" x 6" x 6" obtained a slab of 0.5-1.2 Watts, 22.5-28.5 Amps and 1 Nd: YAG laser set to kHz [Q uantr] Add each slab to Blazer 2000 from ad). I did it. The laser was set to dot matrix mode. The obtained results are the first Shown in the table.

Table 1 1100% O-NM 298%02% -NM 399%1% -VL 497% 1% 2% -L 5 97% 1% 2% -L 5 97% 1% 2% L 7 97% 1 ivy 2% L 892% 1% 7% VL 998%2% -VL 1096% 2% 2% M 1196% 2% 2% G 1297%3% L 1395% 3% 2% --VG 1495% 3% 2% -8 1595% 3% 2% 6 1695% 3% 2% E 1790% 3% 7! %VG 1895% 5% L' 1993% 5% 2% G 2088% 5 pieces 7% L (Note) NM: No mark L; pale mark vL: very faint mark G: Good mark vG: very good mark E: Excellent mark Example 2 Fluorinated ethylene/propylene copolymer (FEP) (commercially available from DuPont), diacid Titanium chloride and organic compounds in the amounts shown in Table ①, with a 60cc mixing pole. Mix in a Gravender internal mixer at 335°C and 50 rpm. The compositions were prepared by pressing each test sample at 335° C. to 0.05°C. A slab measuring 0.25" x 6" x 6" was obtained. Dot matrix mode N set at 0.72-1.5 Watts, 25-33 Amps, 1kHz at d: YAG laser [Blazer 2000] with each step I exposed my love. The results obtained are shown in Table ①.

Table ■ 1100% --NM 297% 3% -NM 395% 3% 2% L (Note’) NM: No mark L: Light mark international search report international search report

Claims (35)

[Claims] 1. Fluoropolymers, fluoropolymers having a processing temperature of about 250°C or higher a compound capable of absorbing about 2-7% by weight of energy from a laser; and about 1 to 15% by weight based on the weight of the fluoropolymer. The mark-enhancing organic compound has a decomposition temperature higher than the processing temperature of the laser. A laser markable composition capable of undergoing a visible color change when exposed to laser. 2. Fluoropolymers include homopolymers and copolymers of tetrafluoroethylene. homopolymers and copolymers of pinylidene fluoride, perfluorinated Consisting of alkoxy polymers and fluorinated ethylene/propylene copolymers The composition of claim 1, wherein the composition is selected from the group. 3. The fluoropolymer is an ethylene/tetrafluoroethylene copolymer. The composition according to claim 2. 4. A composition according to claim 1, wherein the energy absorbing compound is titanium dioxide. 5. The organic compound is a sulfur-containing compound, a hydroxy-containing compound, a nitrogen-containing compound, selected from the group consisting of phosphorus-containing compounds and carbonyl-containing compounds; The composition according to claim 1 or 4. 6. The organic compound is tetrakis[methylene-3-(3,5-di-t-butyl-4 -Hydroxyphenyl)propionate] methane, distearylthiodipropio nate, tris(2,4-di-t-butylphenyl)-4,4'-phosphite and triallyl isocyanurate. 5. The composition according to 5. 7. Fluoropolymers, fluoropolymers having a processing temperature of about 250°C or higher a compound capable of absorbing about 2-7% by weight of energy from a laser; and about 1 to 15% by weight based on the weight of the fluoropolymer. The mark-enhancing organic compound has a decomposition temperature higher than the processing temperature of the laser. The surface is coated with a fluoropolymer composition that can undergo a visible color change when exposed to Items covered. 8. 8. The article of claim 7, which is an electrical conductor. 9. 8. The article of claim 7 which is a wire or cable. 10. Fluoropolymers include homopolymers and copolymers of tetrafluoroethylene. remer, homopolymers and copolymers of pinylidene fluoride, perfluoride Made from loalkoxy polymers and fluorinated ethylene/propylene copolymers. 8. The article of claim 7, wherein the article is selected from the group consisting of: 11. the fluoropolymer is an ethylene/tetrafluoroethylene copolymer The article according to claim 10. 12. 8. The article of claim 7, wherein the energy absorbing compound is titanium dioxide. 13. The organic compound is a sulfur-containing compound, a hydroxy-containing compound, a nitrogen-containing compound, selected from the group consisting of phosphorus-containing compounds and carbonyl-containing compounds; The article according to claim 7 or 12. 14. The organic compound is tetrakis[methylene-3-(3,5-di-t-butyl- 4-Hydroxyphenyl)propionate] methane, distearylthiodipropyl onate, tris(2,4-di-t-butylphenyl)-4,4'-phosphite and triallyl isocyanurate. Item described in item 13. 15. Fluoropolymers, fluoropolymers with a processing temperature of about 250°C or higher Compounds that can absorb energy from about 2-7% by weight of the laser, based on the weight of , and about 1 to 15% by weight based on the weight of the fluoropolymer. The mark-enhancing organic compound has a decomposition temperature higher than the processing temperature of the marker. Formed from a fluoropolymer composition that can undergo a visible color change when exposed to heat-recoverable articles. 16. The heat-recoverable article according to claim 15, which is a tubular article. 17. 17. The heat recoverable article according to claim 16, which is a marker sleep. 18. Fluoropolymers include homopolymers and copolymers of tetrafluoroethylene. remer, homopolymers and copolymers of pinylidene fluoride, perfluoride Consisting of loalkoxy polymers and fluorinated ethylene/propylene copolymers 16. The article of claim 15, wherein the article is selected from the group. 19. the fluoropolymer is an ethylene/tetrafluoroethylene copolymer The composition according to claim 18. 20. 16. The composition of claim 15, wherein the energy absorbing compound is titanium dioxide. 21. Organic compounds include sulfur-containing compounds, hydroxy-containing compounds, and nitrogen-containing compounds , phosphorus-containing compounds and carbonyl-containing compounds. 21. A composition according to certain claims 15 or 20. 22. The organic compound is tetrakis[methylene-3-(3,5-di-t-butyl- 4-Hydroxyphenyl)propionate] methane, distearylthiodipropyl onate, tris(2,4-di-t-butylphenyl)-4,4'-phosphite and triallyl isocyanurate. Item 22. The composition according to item 21. 23. fluoropolymer and about 2-7% by weight based on the weight of the fluoropolymer Compounds that can absorb energy from lasers, and the weight of fluoropolymers from about 1 to 15% by weight based on the decomposition temperature above the processing temperature of the fluoropolymer. Reproducing a fluoropolymer comprising mixing a mark-enhancing organic compound with A method that enables mark formation by a user. 24. Fluoropolymers include homopolymers and copolymers of tetrafluoroethylene. remer, homopolymers and copolymers of pinylidene fluoride, perfluoride Made from loalkoxy polymers and fluorinated ethylene/propylene copolymers. 24. The method of claim 23, wherein the method is selected from the group consisting of: 25. the fluoropolymer is an ethylene/tetrafluoroethylene copolymer 25. The method according to claim 24. 26. 24. The method of claim 23, wherein the energy absorbing compound is titanium dioxide. 27. Organic compounds include sulfur-containing compounds, hydroxy-containing compounds, and nitrogen-containing compounds , phosphorus-containing compounds and carbonyl-containing compounds. 27. The method of claim 23 or 26. 28. The organic compound is tetrakis[methylene-3-(3,5-di-t-butyl- 4-Hydroxyphenyl)propionate] methane, distearylthiodipropyl onate, tris(2,4-di-t-butylphenyl)-4,4'-phosphite and triallyl isocyanurate. The method according to item 27. 29. Based on the weight of the fluoropolymer, the fluoropolymer composition has about 2 to 7 wt% compounds that can absorb energy from lasers, and fluoropolymers Decomposition above the processing temperature of the fluoropolymer of about 1 to 15% by weight based on the weight of A mark-enhancing organic compound having a temperature is included, and the surface of the composition is exposed to a laser. forming a mark on a surface comprising a fluoropolymer composition comprising: forming a mark on a surface comprising a fluoropolymer composition; how to. 30. 30. The method of claim 29, wherein the surface is exposed to a Nd:YAG laser. 31. Fluoropolymers include homopolymers and copolymers of tetrafluoroethylene. remer, homopolymers and copolymers of pinylidene fluoride, perfluoride Made from loalkoxy polymers and fluorinated ethylene/propylene copolymers. 30. The method of claim 29, wherein the method is selected from the group consisting of: 32. the fluoropolymer is an ethylene/tetrafluoroethylene copolymer 32. The method of claim 31. 33. 30. The method of claim 29, wherein the energy absorbing compound is titanium dioxide. 34. Organic compounds include sulfur-containing compounds, hydroxy-containing compounds, and nitrogen-containing compounds , phosphorus-containing compounds and carbonyl-containing compounds. 34. The method of claim 29 or 33. 35. The organic compound is tetrakis[methylene-3-(3,5-di-t-butyl- 4-Hydroxyphenyl)propionate] methane, distearylthiodipropyl onate, tris(2,4-di-t-butylphenyl)-4,4'-phosphite and triallyl isocyanurate. The method according to item 34.